The present invention relates to a vinylidene fluoride resin monofilament and a production method thereof.
A monofilament made of vinylidene fluoride resin is of use as a material, for example, for fishing lines, fishing nets, rope materials, and so on because of its excellent physical and chemical properties, particularly, the properties including excellent mechanical strength and durability, little swelling with water leading to little degradation of strength in water, and so on. Among these uses, the filament, particularly, for the fishing lines is required to have the property of leaving less xe2x80x9ctwistingxe2x80x9d or xe2x80x9ccurlingxe2x80x9d due to a winding propensity and the property of easily relieving the winding propensity, the property of demonstrating high mechanical strength, e.g., knot strength with a knot in the filament, and so on.
The conventional vinylidene fluoride resin monofilaments applied to the fishing lines required to satisfy such various properties include, for example those described in 1) Japanese Patent Application Laid-Open No. 10-298825 filed by Applicant, 2) Japanese Patent Applications Laid-Open No. 04-91215 and No. 07-138810, 3) Japanese Patent Application Laid-Open No. 11-131320 filed by Applicant, and so on.
Incidentally, in order to enhance the knot strength of the vinylidene fluoride resin monofilament, an effective way is to increase the drawing ratio in production to orient the filament in high degree of orientation, but the highly oriented monofilament tends to have the winding propensity easier. The vinylidene fluoride resin monofilament described in above 1) was improved in the winding propensity by setting of the low drawing ratio in production, but this resulted in insufficient improvement in the knot strength.
On the other hand, the vinylidene fluoride resin monofilaments described in above 2) were intended for improvement in the knot strength or improvement in wear resistance, but were not intended for improvement in the winding propensity. Further, the vinylidene fluoride resin monofilament described in above 3) was one obtained by subjecting a highly oriented monofilament in a fixed length state to a thermal treatment at a fixed temperature for a fixed period of time. This achieved the improvement in the winding propensity while preventing the degradation of mechanical strength. However, this thermal treatment in the fixed length state had to be carried out with the use of a large-diameter bobbin over a long period of time, and the batch treatment raised the problem of degradation of productivity.
Therefore, the present invention has been accomplished under such circumstances and an object of the present invention is to provide a vinylidene fluoride resin monofilament and a production method thereof capable of increasing the production efficiency while achieving both satisfactory knot strength and improving capability of the winding propensity.
In order to achieve the above object, the inventors have conducted elaborate research and found out the relaxation thermal treatment conditions for satisfactorily restraining the degradation of the knot strength. From the viewpoint associated with the properties of the vinylidene fluoride resin monofilament, the inventors found that a vinylidene fluoride resin monofilament satisfying a predetermined knot strength according to the filament size and having a predetermined knot elongation and linear elongation is excellent in the improving capability of the winding propensity, thus accomplishing the present invention.
Namely, a vinylidene fluoride resin monofilament according to the present invention is a vinylidene fluoride resin monofilament comprising a vinylidene fluoride resin and satisfies the relation represented by Eq (1) below;
Yxe2x89xa7d3xc3x972xc3x9710xe2x88x927xe2x88x92d2xc3x972xc3x9710xe2x88x924+dxc3x971.17xc3x9710xe2x88x922+73.11xe2x80x83xe2x80x83(1),
wherein a knot elongation is not less than 24% and a straight elongation is not less than 30%. In the equation, d indicates the diameter (xcexcm) of the monofilament, and Y a knot strength (kgf/mm2) thereof.
It was proved that such a vinylidene fluoride resin monofilament had the sufficient knot strength comparable to those of the conventional monofilaments and enhanced its improving capability of the winding propensity. Here the diameter d of the monofilament is preferably 0.05-1.85 mm and more preferably 290-550 xcexcm.
A production method of the vinylidene fluoride resin monofilament according to the present invention is a production method suitable for production of the vinylidene fluoride resin monofilament of the present invention, which comprises a drawing step of drawing a melt-spun vinylidene fluoride resin monofilament; and a dry thermal relaxation treatment step of subjecting the vinylidene fluoride resin monofilament thus drawn, to a relaxation thermal treatment in a gas phase at a temperature between 220xc2x0 C. inclusive and 300xc2x0 C., preferably between 250 and 290xc2x0 C., and under such conditions that a relaxation rate falls between 4% inclusive and 10%, preferably between 7 and 9%, and that a passing time is not more than 5 seconds, preferably between 1 and 5 seconds. In the normal relaxation thermal treatment, the degradation of the mechanical strength, e.g., the knot strength, tends to become more prominent with increase in the relaxation rate. In contrast to it, according to the present invention, the knot strength of the vinylidene fluoride resin monofilament before the relaxation thermal treatment is maintained or is little degraded even if the relaxation rate is so high as in the above range, and the improving capability of the winding propensity is enhanced.
Further, it is extremely preferable for the production of the vinylidene fluoride resin monofilament of the present invention that in the drawing step, the melt-spun vinylidene fluoride resin monofilament is drawn at a drawing ratio of not less than 5.9, more preferably 5.9-6.2.
The terms xe2x80x9cstraight elongation,xe2x80x9d xe2x80x9cknot strength,xe2x80x9d xe2x80x9cknot elongation,xe2x80x9d and xe2x80x9cpassing timexe2x80x9d in the present invention are values defined as below. If the drawing process involves two or more stages of drawing, the xe2x80x9cdrawing ratioxe2x80x9d refers to a total value of drawing ratios in respective stages, i.e., an overall drawing ratio at an end of the drawing process.
 less than Straight elongation greater than : ultimate elongation under ordinary temperature of a sample filament drawn with TENSILON/UTM-III-100 available from TOYO BALDWIN Co., LTD and under the conditions of the chuck-chuck distance (sample length) of 30 cm and the drawing speed (head speed) of 30 cm/min.
 less than Knot strength and knot elongation greater than : breaking tenacity and elongation of a sample filament with a knot in central part of the sample length, drawn as in the measurement of the foregoing straight elongation.
 less than Passing time greater than : time in which a predetermined portion of the vinylidene fluoride resin monofilament passes through the gas phase or for which it stays in the gas phase.
Best Mode for Carrying Out the Invention
The following will describe the preferred embodiments of the vinylidene fluoride resin monofilament and production method thereof according to the present invention.
Vinylidene Fluoride Resin
A homopolymer of vinylidene fluoride can be preferably used as the vinylidene fluoride resin used in the present invention. Without having to be limited to this, other applicable vinylidene fluoride resins include copolymers of a vinylidene fluoride monomer and one or more monomers copolymerizable therewith; mixtures of these copolymers with the homopolymer of vinylidene fluoride; and so on.
Examples of the monomers copolymerizable with vinylidene fluoride include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, vinyl fluoride, and so on, which can be used singly or in a mixed state of two or more monomers. The content of vinylidene fluoride units in these vinylidene fluoride resins is preferably not less than 50 mol %, more preferably not less than 60 mol %, and particularly preferably not less than 80 mol %.
The vinylidene fluoride resin is desired to have such a degree of polymerization that the inherent viscosity (logarithmic viscosity number at 30xc2x0 C. of a solution in which 4 g of the resin is dissolved in 1 l of N,N-dimethylformamide; which will be referred to hereinafter as xe2x80x9cxcex7inhxe2x80x9d) falls preferably in the range of 0.5 to 2.0 dl/g and more preferably in the range of 1.0 to 1.8 dl/g.
Further, the vinylidene fluoride resin as a raw material for the vinylidene fluoride resin monofilament of the present invention may contain one or more selected from the following group in an amount not impairing its properties: additives such as various organic pigments and others; polyester base plasticizers; phthalate base plasticizers; nucleating agents typified by flavanthrone; compositions containing a resin with high compatibility with the vinylidene fluoride resin, e.g., poly((meth)acrylic acid ester), polycarbonate, polyester, a methyl acrylate-isobutylene copolymer, or the like; and so on. The content of the vinylidene fluoride resin in such compositions is preferably not less than 60% by mass and more preferably not less than 70% by mass.
Preferable examples of the foregoing plasticizers are polyesters having repeating structural units of an ester comprised of a C2-C4 diol and a C4-C6 dicarboxylic acid, having a terminal group of a C1-C3 monovalent acid residue or monovalent alcohol residue, and having the molecular weight of 1500-4000.
Vinylidene Fluoride Resin Monofilament
The vinylidene fluoride resin (hereinafter referred to xe2x80x9cPVDFxe2x80x9d on behalf of the resin) monofilament of the present invention is constructed of a single layer or plural layers and at least the surface layer (sheath) thereof is made of PVDF. Namely, the monofilament may be comprised of a single layer of PVDF, or may be comprised of plural layers, wherein an internal layer (core) is comprised of a single layer or plural layers made of thermoplastic resin except for PVDF, e.g., polyamide, polyolefin, or the like and wherein the outermost layer (sheath) is made of PVDF. Preferably, the whole of the monofilament is made of PVDF in either case where the monofilament is constructed of a single layer or plural layers.
The PVDF monofilament of the present invention satisfies the relation represented by Eq (1) below;
Yxe2x89xa7d3xc3x972xc3x9710xe2x88x927xe2x88x92d2xc3x972xc3x9710xe2x88x924+dxc3x971.17xc3x9710xe2x88x922+73.11xe2x80x83xe2x80x83(1),
where d (xcexcm) is the filament size (diameter) thereof and Y (kgf/mm2) the knot strength, and the PVDF monofilament of the present invention has the knot elongation of not less than 24% and the straight elongation of not less than 30%.
If the knot strength in Eq (1) is less than the value given by the right side in the equation, there is an increasing tendency to become hard to satisfy the sufficient knot strength required for the filament size; specifically, for example, when a knot is formed in a leader or a fed part of a fishing line, there is a tendency to cause fracture easily at the knot. Further, if the knot elongation is less than 24% and if the straight elongation is less than 30%, it tends to be hard to satisfactorily absorb impact when a fish or the like takes a fish hook coupled to a fishing line, particularly, impact in an initial stage of taking or during biting, and the line becomes easier to curl and tends to resist correction for curling.
Conversion of units of strength can be made based on the relation represented by 1 kgf/mm2≈9.80665 MPa, and Eq (1) can be converted into the Pa unit, i.e., the relation represented by Eq (2) below;
yxe2x89xa7d3xc3x971.96xc3x9710xe2x88x926xe2x88x92d2xc3x971.96xc3x9710xe2x88x923+dxc3x971.15xc3x9710xe2x88x921+717xe2x80x83xe2x80x83(2).
In this equation, d indicates the filament size (diameter) (xcexcm) and y the knot strength (MPa).
There are no specific restrictions on the filament size (diameter), but d in Eq (1) above is preferably in the range of 52 xcexcm (corresponding to Number 0.1 of fishing line) to 1.81 mm (corresponding to Number 120) and particularly preferably in the range of 50 to 1000 xcexcm.
It was verified with the PVDF monofilament of the present invention satisfying the various conditions as described above that it had the knot strength comparable to those of the conventional filaments and demonstrated significant improvement in the winding propensity. Therefore, when the monofilament is applied to a fishing line, there remains little winding after it is wound on a cylindrical member such as a spool or the like, and it is excellent in the improving capability of the winding propensity even if there occurs twisting or curling due to the winding propensity. Accordingly, slack is reduced in the fishing line put in water, so as to enhance sensitivity to xe2x80x9cstrikexe2x80x9d (bite). Further, the property of less twisting can enhance handleability and, particularly, the handleability is remarkably improved when the PVDF monofilament of small diameter is handled in a long unit.
The following will describe the preferred embodiment of the production method of the PVDF monofilament according to the present invention. First, a mixed composition of the aforementioned vinylidene fluoride resin and plasticizer and others is melted and extruded to form pellets thereof. These pellets are charged into a melt extruder having a predetermined size, e.g., 20-40 mm"PHgr" and a monofilament is melt-spun at a predetermined resin temperature, e.g., at 240-310xc2x0 C. by the extruder. Subsequently, the melt-spun monofilament is cooled in a coolant bath (e.g., a water bath at the temperature of 30 to 60xc2x0 C.) to obtain an undrawn PVDF monofilament.
Here a PVDF monofilament consisting of a single layer can be made of a single kind of vinylidene fluoride resin, and a PVDF monofilament consisting of plural layers can be made of materials selected from vinylidene fluoride resins with different or close compositions, viscosities, additives, etc., other resins, compositions containing either of these, or mixtures of these resins or compositions. As described previously, in the case of the PVDF monofilament comprised of plural layers, the sheath can be made of the vinylidene fluoride resin or a composition thereof, and the core can be made of one selected from the vinylidene fluoride resins, other resins, compositions containing either of these, or mixtures of these resins or compositions.
Subsequently, the resultant undrawn PVDF monofilament is then drawn in a heating medium bath (e.g., a glycerin bath at the temperature of 150-170xc2x0 C.), e.g., at the drawing ratio of about 5-6 (first stage drawing). This is further drawn in a heating medium bath (e.g., a glycerin bath at the temperature of 160-175xc2x0 C.), e.g., at the drawing ratio of about 1-1.2 (second stage drawing). In this way, the drawing step is comprised of the first stage drawing and the second stage drawing.
There are no specific restrictions on the overall drawing ratio in this drawing step, but it is desirable in the present invention that the drawing ratio be preferably not less than 5.9 and more preferably not less than 6. This enhances the degree of orientation of molecular chains in the vinylidene fluoride resin, which is suitable for the production of the PVDF monofilament of the present invention with the foregoing sufficient knot strength (cf. Eq (1)). The drawing ratio can be appropriately selected according to the knot strength required of each fishing line.
Then the drawn PVDF monofilament is subjected to a relaxation thermal treatment in a gas phase (e.g., air, an inert gas, or the like) at the temperature between 220xc2x0 C. inclusive and 300xc2x0 C., preferably between 250 and 290xc2x0 C., and under such conditions that the relaxation rate falls between 4% inclusive and 10%, preferably between 7 and 9%, and that the passing time is not more than 5 seconds, preferably between 1 and 5 seconds (dry thermal relaxation treatment step).
If the above gas phase temperature is less than 220xc2x0 C., it is difficult to achieve the relaxation rate of 4%, which will result in failure in enhancing the knot elongation or the straight elongation satisfactorily and a tendency to fail to achieve the sufficient improving effect of the winding propensity. If the gas phase temperature exceeds 300xc2x0 C. on the other hand, there appears a tendency that the degradation becomes prominent in the mechanical strength, e.g., the knot strength. When the aforementioned relaxation rate is less than 4%, the winding propensity and elongation tend not to be improved well, as described above. When the relaxation rate is 10% or more on the other hand, the knot strength can be heavily degraded. Further, when the foregoing passing time exceeds five seconds, the PVDF monofilament can be melted, depending upon the melting point of the vinylidene fluoride resin.
The production method of the PVDF monofilament according to the present invention can satisfactorily restrain the degradation of the mechanical strength, e.g., the knot strength of the drawn PVDF monofilament, as compared with the conventional relaxation thermal treatment, and can maintain the mechanical strength of the PVDF monofilament enhanced by the drawing, at an excellent level. In addition, the improving capability of the winding propensity can be enhanced, and it is thus feasible to obtain the PVDF monofilament extremely suitable for the fishing lines.
Further, the relaxation thermal treatment as described above can improve the winding propensity while preventing the degradation of the knot strength, thereby providing the PVDF monofilament with excellent properties equivalent to or higher than those achieved by the conventional fixed-length thermal treatment. In production of a long monofilament like the fishing line, the filament can be made in a continuous process, without the need for the batch long-time thermal treatment with the use of the large-diameter bobbin. The production efficiency of the PVDF monofilament can be remarkably increased accordingly.
It is also possible to carry out a relaxation thermal treatment of thermally relaxing the drawn PVDF monofilament in a heating medium such as hot water, hot air, or the like (e.g., at the temperature of about 85xc2x0 C.), prior to the aforementioned dry thermal relaxation treatment step.